Utilizing sulfur-containing petroleum.



J. E. EGGLESTON. I UTILIZING SULFUR CONTAINING PETROLEUM. APPLICATION FILED AUG. 21. 1903.

1, 1 4 Patented Feb. 20,1912.

f snwwu l mm X 774% 6 tnnrnn STATES PATENT OFFICE.

JOHN E. EGGLESTON. 0F BAYONNE, NEW JERSEY, ASSIGNOR TO STANDARD OIL COM- PANY, 0F BAYONNE; NEW JERSEY, A CORPORATION OF NEW JERSEY.

Specification of Letters Patent.

Patented Feb. 20, 1912 Application filed August 21, 1903. Serial No. 170,357.-

T 0 all whom it may concern:

Be it known that I. J 011x E. EGGLESTON, a citizen of the Ynited States, residing at Bayonne. in the county of Hudson and State of New Jersey, have invented certain new and useful Improvements in I -tilizing Sulfur Containing Petroleum: and I do'hereby declare the following to be a full, clear, and exact description of the invention. such as will enable othersskilled in the art to which it appertains to make and use the same.

This invention relates more particularly to the utilization of the sulfur content of such petroleum /as is obtained from the oil fields in the State of Texas, near the town of Beaumont. in Jefferson county. This oil differs from Pennsylvania petroleum (among other respects) in that it contains a notable quantity (between one and two per cent. according to my experience) of sulfur; whereas. Pennsylvania oil is comparatively free from this element. .It differs from Lima. Ohio. oil. which also contains a notable amount of sulfur. in that the sulfur exists in Beaumont oil in such form .that it can be evolved as hydrogen sulfid, whereas, in the case of Lima oil it takes other forms.

The expression Beaumont oil or Beaumont petroleum is used herein for convenience of reference to indicate, not only the oil found near Beaumont, but oil of sub,- stantially similar composition wherever found or however obtained. In such oil the sulfur is chiefly in the form of elementary sulfur in solution in the crude oil. On appropriate heating mostof it unites with hydrogen of hydrocarbons to form hydrogen sulfid; which escapes as gas. Some Of the elementary sulfur is believed to be con verted into sulfur-containing hydrocarbons; but the fact is not important to the present invention. In addition to elementary sulfur in solution in the hydrocarbon liquid, Beaumont petroleum (according to my experience) also has naturally present therein some hydrogen sulfid and some sulfur-containing hydrocarbons. The naturally present hydrogen sulfid is small in amount in comparison with what is formed artificially from the sulfur which is present in elementary form. The naturally present and artificially formed sulfur-containing h drocarhons are not utilizable readily for their sulfnr contents; as they distil over with little decomposition and are of like boiling points with unsulfured hydrocarbons of the pet-roleum; so that in distillation they accompany these unsulfured hydrocarbons and are present with them in the distillates. Hydrogen sulfid, on "the other hand, is a gas liquefiable only under high pressure or at low temperature: so that it does not condense under the conditions which obtain inthe condensers for petroleum vapors.

It is evidentwthat there may be oil otherwise substantially different in composition from Beaumont oil, but analogous thereto in containing naturally a notable quantity of sulfur which can be evolved as hydrogen sulfid.

The invention extends to the utilization of such analogous petroleum'as well as of Beau- 11'1ont-1; eti'oleum itself. I

I have discovered that by passing a continuous stream of the sulfur-containing crude Beaumont oil through a still whose tempera-' ture is maintained at a suitable degree (between 300 F. and 500 a continuous and steady flow of hydrogen sulfid can be obtained of suflicient purity (over 96% hydrogen sulfid) when deprived of oil vapors passing over with it to be used for the -pro-' duction of sulfuric acid by known meaiis.

Such a steady and continuous flow of hydrogen sulfid is important to the commercial manufacture therefrom of sulfuric acid. Further. I have discovered that the evolution of the very pure gas '(of 96% or over hydrogen sulfid) is preceded and followed by a less pure gas, and that by the use of a series of three continuous stills at gradually-increasing temperatures theless pure gas (about 84% or 85% hydrogen sulfid) can be obtained from the end stills, wliile the middle still is furnishing a steady and continuous flow of the very pure gas. Still further, in the industrial production of hydrogen sulfid from Beaumont oil, I have found it important so to adjust the respective temperatures of the three stills as that the evaporation of hydrocarbons (which attends the heating of the oil to the temperature requisite to evolve hydrogen sulfid) takes place more largely in the end stills than in the middle one, in which the work performed is more largely the evolution of the hydrogen sulfid. By this distribution not only can the work (or, in other words, the absorption of energy jointly by the oil and the aeriform products) be made more nearly uniform in the respective stills, but the difference between the respective temperatures of the infiowing and outfiowing oil may be less for the middle still than it otherwise would be.

Any known or suitable mode of continuously heating a stream of oil can be employed; but I have employed, and I consider it an advantage and special improvement to employ, that mode in which a compact body (of several barrels volume at a minimum) of oil is maintained, into and out of which body flows a stream of oil. More over, it is considered important to conduct the outfiowing stream from the bottom of said compact body, which besides is best elongated after the manner of the liquid contents of an elongated horizontally disposed and partly filled cylinder. Still further, I have found it important to inject free steam into the oil in order to remove therefrom a certain amount of hydrogen sulfid which would be liable to remain in the residual oil from the last still. Apparently this hydrogen sulfid exists as such in solution in the oil, and consists at least in part of the product of the heating operation.

In producing hydrogen sulfid from Beaumont oil, the latter necessarily parts with so much of its sulfur content as is represented in the hydrogen sulfid given off. Some sulfur will still be present in the oil; but to effect a substantial, although partial, desulfuration of Beaumont or analogous petroleum by continuous heating as above explained is considered a special feature of invention as being an advantageous mode of eflecting such result, irrespective of the utilization of the sulfur content of the evolved gas. Moreover, in freeing the hydrogen sulfid from oil vapors, a utilizable distillate is obtained consisting of lighter hydrocarbons of the burning oil fraction.

To utilize the hydrogen sulfid evolved from Beaumont petroleum for the production of sulfuric acid (which is to be taken as including sulfuric anhydrid as well as fuming or non-fuming acid of any desired degree of hydration) the evolved gas can be burned .(in any known or suitable hydrogen sulfid burner, for example) and the products of combustion, with or without removal of the water therefrom, be subjected to opera tions for oxidizing sulfur dioXid (in any known or suitable form of lead chambers or of contact apparatus, for example).

The gas evolved from the crude oil can be subjected to other operations for utilizing its sulfur content. For example, without being burned, it can be made to deposit sulfur by reaction with sulfur dioxid; or, after being burned, the products of combustion can be made to deposit sulfur by reaction with hydrogen sulfid, or to produce various sulfur dioxid products (sulfite and bisulfite salts, or sulfurous acid solutions, for example) by subjecting the products of combustion to known or suitable operations for the purpose.

Any appropriate apparatus can be used to carry the invention into effect.

A suitable apparatus, itself of my invention, is illustrated in the accompanying drawing; but, in consequence solely of official requirement of division, said apparatus (which was originally claimed herein) is made the subject of my application No. 363.868 filed March 22, 1907, as a division and continuation hereof. Patent 908,400 was granted December 29, 1908, on said divisional application.

Figure 1 is a diagram of such apparatus, and Fig. 2 a vertical longitudinal section of one of the stills.

The crude sulfur-bearing Beaumont petroleum, or an analogous crude oil, is supplied by pipe a to the inlet end of the horizontally disposed cylinder still I), this latter being the first of a series of four fire heated stills. It fills the still I) to above its firing line, and overflows from its outlet end by the pipe 0, which conveys it to the inlet end of the still (I. It similarly fills still (Z and overflows from its out-let end by the pipe 6, which conveys itto the inlet end of the still f, from which it overflows at the outlet end thereof by the pipe 5 into still it, at its inlet end. From the outlet end of still h it overflows by the pipe 2'. The supply pipe a, the overflow and supply pipes c e g, and the overflow pipe 1' are so arranged that the oil flows by gravity through the stills b, d, f, It. These should each hold several barrels of oil at a minimum. Stills with a charging capacity of six hundred barrels (forty gallons to the barrel) of oil measured at 60 F. have been found eflicient. In running the still 6 may hold 610 barrels, the still (Z 580 barrels,

and the stills f and h 500 barrels each of oil measured at the respective still temperatures. The several stills being heated, vapors and gas pass off by the goose-necks, j, is, Z, m, to the corresponding condensing worms 11-, 0, 7), q, wherein the vapors and gas are so cooled as to reduce the vapors to the liquid state and thus to separate them from the The liquids pass off by the pipes r, s, t, u. The gas passes off by the pipes v, u, m, 11 to the gas line 2, which conveys the gas to the apparatus for utilizing its sulfur content. The gas pipe for each worm has a branch 2, 3, 4, 5, respectively, into which the gas is made to'pass. by appropriate valves, whenever it becomes too impure for satisfactory utilization for its content of sulfur, instead of being allowed to proceed to the gas line 2. The gas thus switched off can be burned as fuel or disposed of in any desired way.

The heating of the several stills is regulated as follows: the still 5 in such manner that the oil near the outlet has a temperature of about 350 F., more or less; the still Free steam (ordinary live steam from a boiler, or it may be exhaust steam, or steam more or less superheated) is let through pipe 7 into the body of oil in still h in small quantity, say, ten pounds of water in the form of steam to each hundred pounds of crude oil admitted into still I).

The hydrocarbons are evaporated less and the hydrogen sulfid evolved more in the still d than in those (I) and f) which precede and follow it; and the hydrogen sulfid from these latter is less pure than that from the middle still (Z of the series ofthree. Ac: cording to my experience, the gas from stills b and f should be about 84% or 85% hydrogen sulfid, while that from still (Z should be over 96% this substance.

The gas from pipe line 2 is delivered to a hydrogen sulfid burner 8, by the combustion in which sulfur dioxid and water (with insignificant amounts of carbonic acid from hydrocarbons present) are produced. The products of combustion pass to the lead chamber 9, wherein the sulfur dioxid is oxidized to sulfuric acid in the known man ner. The said combustion products can be sentthrough a Glover tower 10 on their way to the lead chamber; but, on accountof the large amount of water vapor present, this is notrecommended. The dilute chamber acid can bekoncentrated in any known or suitable way. The products from burning the hydrogen sulfid, instead of being sent into a lead chamber, could (after being suitably freed by known methods from more or less of the water vapor therein) be sent into a contact apparatus for oxidizing the sulfur dioxid in the known way; or if it should be desired to utilize said products otherwise than in making sulfuric acid, they could be subjected to appropriate known operations in any known or suitable apparatus for the purpose. If it should be desired to utilize the hydrogen sulfid, without burning. the gas from the worms n. 0. p, 9.

The distillates from the worms n, 0, p and q consist each of lighter hydrocarbons belonging to the burning oil fraction of the Beaumont or analogous petroleum.- In my experience those from the worms n and 0 can be used, in burning oil, after the ordinary sulfuric acid treatment; whereas. the distillates from worms 2 and 9 would have to be made less smoky by other means before they wouldbe suitable for such use, unless they should be added to such a proportion of non-smoking oil as to make a non-smoking mixture. Such a mixture could be made, for example. with Pennsylvania oil. The amount of the nonsmoking about one and six-tenths per cent. in the crude oil. Such reduced oil can be made into burning oil (kerosene) or other petroleum products; or it can'be used as fuel, if this should be found more profitable. In either case it will have been improved by the removal (in part) of its sulfur content.

I claim as my invention or discovery: 1. The lmprovement 1n ut1l1z1ng Beaumont or analogous petroleum. consisting in passing a stream of such sulfur-containing oil through a still maintained at a temperature suflicient to evolve hydrogen sulfid, to wit, between about 300 F and about 500 F.,- cooling the evolved gas to condense and so to separate therefrom the oil vapors burning the gas, and subjecting the products of combustion to operations for converting sulfur dioxid into sulfuric acid, substantially as described.

2. The improvement in utilizing Beaumont or analogous petroleum. consisting in passing a stream of such s1 1lfur-containing oil through a still maintained at a temperature sufficient to evolve hydrogen sulfid. to wit, between about 300 F. and about 500 F., and subjecting the evolved gas to operations as specified for utilizing the sulfur content of hydrogen sulfid, substantially as described.

3. The improvement in utilizing Beaumont or analogous petroleum, consisting in passing a stream of such sulfur-containing oil through a still maintained at a temperature sufficient to evolvehydrogen sulfid, to wit,between about 300 F. and about 500 F., substantially as described.

4. The improvement in utilizing Beaumont or analogous petroleum. consisting in passing a stream of-such sulfur-containing oil through a still maintained aha temperature sufficient to evolve hydrogen sulfid, to wit,between about300 F. and about 500 F., and cooling the evolved gas to'condense and so to separate therefrom the oil vapors, and burning the gas, substantially as described.

5. The improvement in utilizing Beaumont or analogous petroleum, consisting in passing a stream of such sulfur-containing oil through a series of stills maintained at gradually increasing temperatures between about 300 F. and about 500 F., substantially as described.

6. The improvement in utilizing Beaumont or analogous petroleum, consisting in passing a stream of such sulfur-containing oil through aseries of stills maintained. at gradually increasing temperatures between about 300 F. and about 500 1 and separately cooling the gas evolved from the re: spective stills, substantially as described.

7. The improvement in utilizing Beaumont or analogous petroleum, consisting in passing a stream of such sulfur-containing oil through a series of stills maintained at gradually increasing temperatures between about 300 F. and about 500 F., separately cooling the evolved gas from the respective stills, burning the gas as specified, and subjecting the products of combustion to operations for converting sulfur dioxid into sulfuric acid, substantially as described.

8. The improvement in utilizing Beaumont or analogous petroleum, consisting in passing a stream of such sulfur-containing oil through a series of stills maintained at gradually increasing temperatures between about 300 F. and about 500 F., and subjecting the evolved gas to operations as specified for utilizing its sulfur content, substantially as described.

9. The improvement in utilizing Beau- -mont or analogous petroleum, consisting in passing a stream of such sulfur-containing oil through a still maintained at about 400 F cooling the evolved gas to condense and so to separate therefrom the oil vapors, burning the gas, and subjecting the products of combustion to operations for converting sulfur dioxid into sulfuric acid, ubstantially as described.

10. The improvement in utilizing Beaumont or analogous petroleum, consisting in passing a stream of such sulfur-containing oil through a still maintained at about 400 F., and subjecting the evolved gas to operations. as specified for utilizing its sulfur content, substantially as described.

11. The improvement in utilizing Beaumont or analogous petroleum, consisting in passing a'stream of such sulfur-containing oil througha still maintained at about 400 F substantially as described.

12. The improvement in utilizing Beaumont or analogous petroleum, consistmg in passing a stream of'such sulfur-containing oil through a series of stills, one of which is maintained at about 400 F., substantially as described. 14. The improvement in utilizing Beaumont or analogous petroleum, consisting in passing a stream of such sulfur-containing oil through series of stills whose respective temperatures are so adjusted as that largely more hydrogen sulfid is given off in one than in another of the series, substantially as described.

15. The improvement in utilizing Beaumont or analogous petroleum, consisting in heating such sulfur-bearing petroleum to a temperature sufficient to evolve hydrogen sulfid, to .wit, between about 300 F. and about 500 F., afterward exposing the oil tofree steam to eliminate the hydrogen sulfid in solution, cooling the evolved gas to condense and so to separate therefrom the oil vapors, burning the gas, and subjecting the products of combustion to operations for converting sulfur dioXid into sulfuric acid, substantially as described.

16. The improvement in utilizing Beaumont or analogous petroleum, consisting in heating such sulfur-bearing petroleum to a temperature sufficient to evolve hydrogen sulfid, to Wit, between about 300 F. and about 500 F., afterward exposing the oil to free steam to eliminate the hydrogen sulfid in solution, and subjecting the evolved gas to operations as specified for utilizing the sulfur content of hydrogen sulfid, substantially as described.

17. The improvement in utilizing Beaumont or analogous petroleum, consisting in heating such sulfur-bearing petroleum to a temperature sufficient to evolve hydrogen sulfid, to wit, between about 300 F. and about 500 F., and afterward exposing the oil to free steam to eliminate the hydrogen sulfid in solution, substantially as described.

18. The improvement in utilizing Beaumont or analogous petroleum, consisting in heating such sulfur-bearing petroleum to a temperature sufficient to evolve hydrogen sulfid, to wit, between about 300 F. and about 500 F., afterward exposingthe oil to free steam to eliminate the hydrogen sulfid in solution, and cooling the evolved gas to condense and so to separate therefrom the oil vapors, substantially as described.

19. The process of making hydrogen sulfid from Beaumont or analogous petroleum, by passing a stream .of such sulfur containing oil through a still maintained sulfid from Beaumont or analogous petroleum, by passing a stream of such sulfur containing oil through a series of stills maintained at gradually increasing temperatures between about 300 F. and about 500 F., and collecting the so evolved gas appropriately for subsequent subjection of the same to operations as specified forutilizing its sulfur content, substantially as described.

21. The process of making hydrogen sulfid from'Beaumont or analogous petro-- leuin, by passing a stream of such sulfur containing oil through a still maintained,

at about 400 F., and collecting the so evolved gas" appropriately for subsequent subjection of the same to operations as specified for utilizing its sulfur content, substantially as described. a

22. The process of making hydrogen sulfid from Beaumont or analogous petroleum,. by heating such sulfur containing oil operations as specified for utilizing its sulfur content, substantially as described.

In testimony whereof-I aflix my signature in presence of two witnesses.

JOHN E. EGGLESTON,

Witnesses:

I v C. I. ROBINSON, A. P. ARNOLD.

1 to a temperature sufiicient to evolve'hydro- 'gen sulfid to wit, between about 300 F. 

